This invention relates to improvements in preventing heat- and moisture-shrink problems in specific polypropylene fibers. Such fibers require the presence of certain compounds that quickly and effectively provide rigidity to the target polypropylene fiber after heat-setting. Generally, these compounds include any structure that nucleates polymer crystals within the target polypropylene after exposure to sufficient heat to melt the initial pelletized polymer and upon allowing such a melt to cool. The compounds must nucleate polymer crystals at a higher temperature than the target polypropylene without the nucleating agent during cooling. In such a manner, the xe2x80x9crigidifyingxe2x80x9d nucleator compounds provide nucleation sites for polypropylene crystal growth. After drawing the nucleated composition into fiber form, the fiber is then exposed to sufficient heat to grow the crystalline network, thus holding the fiber in a desired position. The preferred xe2x80x9crigidifyingxe2x80x9d compounds include dibenzylidene sorbitol based compounds, as well as less preferred compounds, such as sodium benzoate, certain sodium and lithium phosphate salts (such as sodium 2,2xe2x80x2-methylene-bis-(4,6-di-tert-butylphenyl)phosphate, otherwise known as NA-11). Specific methods of manufacture of such fibers, as well as fabric articles made therefrom, are also encompassed within this invention.
There has been a continued desire to utilize polypropylene fibers in various different products, ranging from apparel to carpet backings (as well as carpet pile fabrics) to reinforcement fabrics, and so on. Polypropylene fibers exhibit excellent strength characteristics, highly desirable hand and feel, and do not easily degrade or erode when exposed to certain xe2x80x9cdestructivexe2x80x9d chemicals. However, even with such impressive and beneficial properties and an abundance of polypropylene, which is relatively inexpensive to manufacture and readily available as a petroleum refinery byproduct, such fibers are not widely utilized in products that are exposed to relatively high temperatures during use, cleaning, and the like. This is due primarily to the high and generally non-uniform heat- and moisture-shrink characteristics exhibited by typical polypropylene fibers. Such fibers are not heat stable and when exposed to standard temperatures (such as 150xc2x0 C. and 130xc2x0 C. temperatures), the shrinkage range from about 5% (in boiling water) to about 7-8% (for hot air exposure) to 12-13% (for higher temperature hot air). These extremely high and varied shrink rates thus render the utilization and processability of highly desirable polypropylene fibers very low, particularly for end-uses that require heat stability (such as apparel, carpet pile, carpet backings, molded pieces, and the like). To date, there has been no simple solution to such a problem. Some ideas have included narrowing and controlling the molecular weight distribution of the polypropylene components themselves in each fiber or mechanically working the target fibers prior to and during heat-setting. Unfortunately, molecular weight control is extremely difficult to accomplish initially, and has only provided the above-listed shrink rates (which are still too high for widespread utilization within the fabric industry). Furthermore, the utilization of very high heat-setting temperatures during mechanical treatment has, in most instances, resulted in the loss of good hand and feel to the subject fibers. Another solution to this problem is preshrinking the fibers, which involves winding the fiber on a crushable paper package, allowing the fiber to sit in the oven and shrink for long times, (crushing the paper package), and then rewinding on a package acceptable for further processing. This process, while yielding an acceptable yarn, is expensive, making the resulting fiber uncompetitive as compared to polyester and nylon fibers. As a result, there has not been any teaching or disclosure within the pertinent prior art providing any heat- and/or moisture-shrink improvements in polypropylene fiber technology.
It is thus an object of the invention to provide improved shrink rates for standard polypropylene fibers. A further object of the invention is to provide a class of additives that, in a range of concentrations, will give low shrinkage. A further object of the invention is to provide a specific method for the production of nucleator-containing polypropylene fibers permitting the ultimate production of such low-shrink fabrics therewith. Accordingly, this invention encompasses a polypropylene fiber possessing at most 5,000 denier per filament and exhibiting a heat-shrinkage in at least 150xc2x0 C. hot air of at most 11%, wherein said fiber further comprises at least one nucleating agent. Also, this invention encompasses a polypropylene fiber possessing at most 5,000 denier per filament and exhibiting a heat-shrinkage in at least 150xc2x0 C. hot air of at most 11%, wherein said fiber further comprises at least one nucleating agent, and wherein said fiber further exhibits a long period of at least 20 nm as measured by small-angle x-ray scattering. Furthermore, this invention encompasses a polypropylene fiber possessing at most 5,000 denier per filament and comprising at least one nucleating agent, and wherein said fiber further exhibits a long period of at least 20 nm as measured by small-angle x-ray diffraction spectroscopy. Additionally, this invention encompasses a polypropylene fiber possessing at most 5,000 denier per filament and exhibiting a peak crystallization temperature of at least 115xc2x0 C. as measured by differential scanning calorimetry in accordance with a modified ASTM Test Method D3417-99 at a cooling rate of 20xc2x0 C./min, and wherein said fiber further exhibits a long period of at least 20 nm as measured by small-angle x-ray scattering. Certain yarns and fabric articles comprising such inventive fibers are also encompassed within this invention.
Furthermore, this invention also concerns a method of producing such fibers comprising the sequential steps of a) providing a polypropylene composition in pellet or liquid form comprising at least 100 ppm by weight of a nucleator compound; b) melting and mixing said polypropylene composition of step xe2x80x9caxe2x80x9d to form a substantially homogeneous molten plastic formulation; c) extruding said plastic formulation to form a fiber structure; d) mechanically drawing said extruded fiber (optionally while exposing said fiber to a temperature of at most 105xc2x0 C.); and e) exposing said drawn fiber of step xe2x80x9cdxe2x80x9d to a subsequent heat-setting temperature of at least 110xc2x0 C. Preferably, step xe2x80x9cbxe2x80x9d will be performed at a temperature sufficient to effectuate the melting of all polymer constituent (e.g., polypropylene), and possibly the remaining compounds, including the nucleating agent, as well (melting of the nucleating agent is not a requirement since some nucleating agents do not melt upon exposure to such high temepratures). Thus, temperatures within the range of from about 175 to about 300xc2x0 C., as an example (preferably from about 200 to about 275xc2x0, and most preferably from about 220 to about 250xc2x0 C., are proper for this purpose. The extrusion step (xe2x80x9ccxe2x80x9d) should be performed while exposing the polypropylene formulation to a temperature of from about 185 to about 300xc2x0 C., preferably from about 210 to about 275xc2x0 C., and most preferably from about 230 to about 250xc2x0 C., basically sufficient to perform the extrusion of a liquefied polymer without permitting breaking of any of the fibers themselves during such an extrusion procedure. The drawing step may be performed at a temperature which is cooler than normal for a standard polypropylene (or other polymer) fiber drawing process. Thus, if a cold-drawing step is followed, such a temperature should be below about 105xc2x0 C., more preferably below about 100xc2x0 C., and most preferably below about 90xc2x0 C. Of course, higher temperatures may be used if no such cold drawing step is followed. The final heat-setting temperature is necessary to xe2x80x9clockxe2x80x9d the polypropylene crystalline structure in place after extruding and drawing. Such a heat-setting step generally lasts for a portion of a second, up to potentially a couple of minutes (i.e., from about {fraction (1/10)}th of a second, preferably about xc2xd of a second, up to about 3 minutes, preferably greater than xc2xd of a second). The heat-setting temperature must be greater than the drawing temperature and must be at least 110xc2x0 C., more preferably at least about 115xc2x0, and most preferably at least about 125xc2x0 C. The term xe2x80x9cmechanically drawingxe2x80x9d is intended to encompass any number of procedures which basically involve placing an extensional force on fibers in order to elongate the polymer therein. Such a procedure may be accomplished with any number of apparatus, including, without limitation, godet rolls, nip rolls, steam cans, hot or cold gaseous jets (air or steam), and other like mechanical means.
In another embodiment of the method of making such inventive fibers, step xe2x80x9ccxe2x80x9d noted above may be further separated into two distinct steps. A first during which the polymer is extruded as a sheet or tube, and a second during which the sheet or tube is slit into narrow fibers of less than 5000 deniers per filament (dpf).
All shrinkage values discussed as they pertain to the inventive fibers and methods of making thereof correspond to exposure times for each test (hot air and boiling water) of about 5 minutes. The heat-shrinkage at about 150xc2x0 C. in hot air is, as noted above, at most 11% for the inventive fiber; preferably, this heat-shrinkage is at most 9%; more preferably at most 8%; and most preferably at most 7%. Also, the amount of nucleating agent present within the inventive fiber is at least 10 ppm; preferably this amount is at least 100 ppm; and most preferably is at least 1250 ppm. Any amount of such a nucleating agent should suffice to provide the desired shrinkage rates after heat-setting of the fiber itself; however, excessive amounts (e.g., above about 10,000 ppm and even as low as about 6,000 ppm) should be avoided, primarily due to costs, but also due to potential processing problems with greater amounts of additives present within the target fibers.
The term xe2x80x9cpolypropylenexe2x80x9d is intended to encompass any polymeric composition comprising propylene monomers, either alone or in mixture or copolymer with other randomly selected and oriented polyolefins, dienes, or other monomers (such as ethylene, butylene, and the like). Such a term also encompasses any different configuration and arrangement of the constituent monomers (such as syndiotactic, isotactic, and the like). Thus, the term as applied to fibers is intended to encompass actual long strands, tapes, threads, and the like, of drawn polymer. The polypropylene may be of any standard melt flow (by testing); however, standard fiber grade polypropylene resins possess ranges of Melt Flow Indices between about 2 and 50. Contrary to standard plaques, containers, sheets, and the like (such as taught within U.S. Pat. No. 4,016,118 to Hamada et al., for example), fibers clearly differ in structure since they must exhibit a length that far exceeds its cross-sectional area (such, for example, its diameter for round fibers). Fibers are extruded and drawn; articles are blow-molded or injection molded, to name two alternative production methods. Also, the crystalline morphology of polypropylene within fibers is different than that of standard articles, plaques, sheets, and the like. For instance, the dpf of such polypropylene fibers is at most about 5000; whereas the dpf of these other articles is much greater. Polypropylene articles generally exhibit spherulitic crystals while fibers exhibit elongated, extended crystal structures. Thus, there is a great difference in structure between fibers and polypropylene articles such that any predictions made for spherulitic particles (crystals) of nucleated polypropylene do not provide any basis for determining the effectiveness of such nucleators as additives within polypropylene fibers.
The terms xe2x80x9cnucleatorsxe2x80x9d, xe2x80x9cnucleator compound(s)xe2x80x9d, xe2x80x9cnucleating agentxe2x80x9d, and xe2x80x9cnucleating agentsxe2x80x9d are intended to generally encompass, singularly or in combination, any additive to polypropylene that produces nucleation sites for polypropylene crystals from transition from its molten state to a solid, cooled structure. Hence, since the polypropylene composition (including nucleator compounds) must be molten to eventually extrude the fiber itself, the nucleator compound will provide such nucleation sites upon cooling of the polypropylene from its molten state. The only way in which such compounds provide the necessary nucleation sites is if such sites form prior to polypropylene recrystallization itself. Thus, any compound that exhibits such a beneficial effect and property is included within this definition. Such nucleator compounds more specifically include dibenzylidene sorbitol types, including, without limitation, dibenzylidene sorbitol (DBS), monomethyldibenzylidene sorbitol, such as 1,3:2,4-bis(p-methylbenzylidene) sorbitol (p-MDBS), dimethyl dibenzylidene sorbitol, such as 1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol (3,4-DMDBS); other compounds of this type include, again, without limitation, sodium benzoate, NA-11, and the like. The concentration of such nucleating agents (in total) within the target polypropylene fiber is at least 100 ppm, preferably at least 1250 ppm. Thus, from about 100 to about 5000 ppm, preferably from about 500 ppm to about 4000 ppm, more preferably from about 1000 ppm to about 3500 ppm, still more preferably from about 1500 ppm to about 3000 ppm, even more preferably from about 2000 ppm to about 3000 ppm, and most preferably from about 2500 to about 3000 ppm. Furthermore, fibers may be produced by the extrusion and drawing of a single strand of polypropylene as described above, or also by extrusion of a sheet, then cutting the sheet into fibers, then following the steps as described above to draw, heat-set, and collect the resultant fibers. In addition, other methods to make fibers, such as fibrillation, and the like, are envisioned for the same purpose.
Also, without being limited by any specific scientific theory, it appears that the shrink-reducing nucleators which perform the best are those which exhibit relatively high solubility within the propylene itself. Thus, compounds which are readily soluble, such as 1,3:2,4-bis(p-methylbenzylidene) sorbitol provides the lowest shrinkage rate for the desired polypropylene fibers. The DBS derivative compounds are considered the best shrink-reducing nucleators within this invention due to the low crystalline sizes produced by such compounds. Other nucleators, such as NA-11, also provide good low-shrink characteristics to the target polypropylene fiber; however, apparently due to poor dispersion of NA-11 in polypropylene and the large and varied crystal sizes of NA-11 within the fiber itself, the shrink rates are noticeably higher than for the highly soluble, low crystal-size polypropylene produced by well-dispersed MDBS.
One manner of testing for the presence of a nucleating agent within the target fibers is preferably through differential scanning calorimetry to determine the peak crystallization temperature exhibited by the resultant polypropylene. The fiber is melted and placed between two plates under high temperature and pressure to form a sheet of sample plastic. A sample of this plastic is then melted and subjected to a differential scanning calorimetry analytical procedure in accordance with modified ASTM Test Method D3417-99 at a cooling rate of 20xc2x0 C./minute. A sufficiently high peak crystallization temperature (above about 115xc2x0 C., more preferably above about 116xc2x0 C., and most preferably above about 116.5xc2x0 C.), well above that exhibited by the unnucleated polypropylene itself, shall indicate the presence of a nucleating agent since attaining such a high peak crystallization without a nucleating agent is not generally possible.
It has been determined that the nucleator compounds that exhibit good solubility in the target molten polypropylene resins (and thus are liquid in nature during that stage in the fiber-production process) provide more effective low-shrink characteristics. Thus, low substituted DBS compounds (including DBS, p-MDBS) appear to provide fewer manufacturing issues as well as lower shrink properties within the finished polypropylene fibers themselves. Although p-MDBS is preferred, however, any of the above-mentioned nucleators may be utilized within this invention as long as the long period (SAXS) measurements are met or the low shrink requirements are achieved through utilization of such compounds. Mixtures of such nucleators may also be used during processing in order to provide such low-shrink properties as well as possible organoleptic improvements, facilitation of processing, or cost.
In addition to those compounds noted above, sodium benzoate and NA-11 are well known as nucleating agents for standard polypropylene compositions (such as the aforementioned plaques, containers, films, sheets, and the like) and exhibit excellent recrystallization temperatures and very quick injection molding cycle times for those purposes. The dibenzylidene sorbitol types exhibit the same types of properties as well as excellent clarity within such standard polypropylene forms (plaques, sheets, etc.). For the purposes of this invention, it has been found that the dibenzylidene sorbitol types are preferred as nucleator compounds within the target polypropylene fibers. Of interest, as well, is the ability to provide a purely liquid formulation of the dibenzylidene sorbitol compounds for introduction within the target polypropylene compositions. Such liquid DBS formulations comprise certain nonionic surfactants that can be selected both for their liquefying and stability-providing benefits to the DBS compounds themselves, but also potentially for their lubricating properties for the eventual fiber. In such a manner, the amount of lubricant generally required for and added to the target fiber may be reduced or eliminated, thus reducing costs associated with such additives. Thus, the surfactants required for such a liquid nucleator composition of 3,4-DMDBS (or other types of nucleating agents), include those which are nonionic and which are ethoxylated to the extent that their hydrophilic-lipophilic balance (HLB) is greater than about 8.5. HLB is a measure of the solubility of a surfactant both in oil and in water and is approximated as one-fifth (⅕) the weight percent of ethoxy groups present on the particular surfactant backbone. More specifically, such surfactants exhibit a HLB value of more preferably greater than about 12, and most preferably greater than about 13, and must possess at least some degree of ethoxylation, more preferably greater than about 4 molar equivalents of ethylene oxide (EO) per molecule, and most preferably greater than about 9.5 molar equivalents of EO per molecule.
Of these preferred surfactants, the most preferred for utilization within the potential fluid nucleating agent dispersion for purposes of this invention include, in tabulated form:
This list is not exhaustive as these are merely the preferred surfactants for use within the potential fluid nucleating agent dispersion for utilization within this invention. In such a fluid dispersion, then, the nucleating agent, such as preferably 3,4-DMDBS, comprises at most 40% by weight, preferably about 30% by weight, of the entire inventive fluid dispersion. Any higher amount will deleteriously affect the viscosity of the dispersion. Preferably the amount of surfactant is from about 70% to about 99.9%, more preferably from about 70% to about 85%; and most preferably, from about 70% to about 75% of the entire inventive fluid dispersion. A certain amount of water may also be present in order to effectively lower the viscosity of the overall liquid dispersion. Optional additives may include plasticizers, antistatic agents, stabilizers, ultraviolet absorbers, and other similar standard polyolefin thermoplastic additives. Other additives may also be present within this composition, most notably antioxidants, antistatic compounds, perfumes, chlorine scavengers, and the like. As noted above, this type of fluid dispersion is disclosed in greater detail within U.S. Pat. Nos. 6,102,999 and 6,127,440, both herein entirely incorporated by reference. Most preferred is a composition of 30% by weight of 3,4-DMDBS and 70% by weight of Tween(copyright) 80. This mixture is listed in the Preferred Embodiments section below as xe2x80x9cLiquid 3,4-DMDBSxe2x80x9d.
The closest prior art references teach the addition of nucleator compounds to general polypropylene compositions (such as in U.S. Pat. No. 4,016,118, referenced above). However, some teachings include the utilization of certain DBS compounds within limited portions of fibers in a multicomponent polypropylene textile structure. For example, U.S. Pat. Nos. 5,798,167 to Connor et al. and 5,811,045 to Pike, both teach the addition of DBS compounds to polypropylene in fiber form; however, there are vital differences between those disclosures and the present invention. For example, both patents require the aforementioned multicomponent structures of fibers. Thus, even with DBS compounds in some polypropylene fiber components within each fiber type, the shrink rate for each is dominated by the other polypropylene fiber components which do not have the benefit of the nucleating agent. Also, there are no lamellae that give a long period (as measured by small-angle X-ray scattering) thicker than 20 nm formed within the polypropylene fibers due to the lack of a post-heatsetting step being performed. Again, these thick lamellae provide the desired inventive higher heat-shrink fiber. Also of importance is the fact that, for instance, Connor et al. require a nonwoven polypropylene fabric laminate containing a DBS additive situated around a polypropylene internal fabric layer which contained no nucleating agent additive. The internal layer, being polypropylene without the aid of a nucleating agent additive, dictates the shrink rate for this structure. Furthermore, the patentees do not expose their yarns and fibers to heat-setting procedures in order to permanently configure the crystalline fiber structures of the yarns themselves as low-shrink is not their objective.
In addition, Spruiell, et al, Journal of Applied Polymer Science, Vol. 62, pp. 1965-75 (1996), reveal using a nucleating agent, MDBS, at 0.1%, to increase the nucleation rate during spinning. However, after crystallizing and drawing the fiber, Spruiell et al. do not expose the nucleated fiber to any heat, which is necessary to impart the very best shrinkage properties, therefore the shrinkage of their fibers was similar to conventional polypropylene fibers without a nucleating agent additive. In the examples below, yarn made with similar levels of nucleating agent additives included and no further heat exposure showed worse shrinkage (at all measured temperatures after the standard 5 minute exposure time) than commercial fibers, and fibers which contained no additive and were exposed to the same conditions. Thus, in addition to the presence of the nucleating agent additive, exposure to heat after mechanical drawing is a crucial step in the invention.
Of particular interest and which has been determined to be of primary importance in the production of such inventive low-shrink polypropylene fibers, is the discovery that, at the very least, the presence of nucleating agent within heat-set polypropylene fibers (as discussed herein), provides high long period measurements for the crystalline lamellae of the polypropylene itself. This discovery is best explained by the following:
Polymers, when crystallized from a melt under dynamic temperature and stress conditions, first supercool and then crystallize with the crystallization rate dependent on the number of nucleation sites, and the growth rate of the polymer, which are both in turn related to the thermal and mechanical working that the polymer is subjected to as it cools. These processes are particularly complex in a normal fiber drawing line. The results of this complex crystallization, however, can be measured using small angle x-ray scattering (SAXS), with the measured SAXS long period representative of an average crystallization temperature. A higher SAXS long period corresponds to thicker lamellae (which are the plate-like polymer crystals characteristic of semi-crystalline polymers like PP). The higher the crystallization temperature of the average crystal, the thicker the measured SAXS long period will be. Further, higher SAXS long periods are characteristic of more thermally stable polymeric crystals. Crystals with shorter SAXS long periods will xe2x80x9cmeltxe2x80x9d, or relax and recrystallize into new, thicker crystals, at a lower temperature than those with higher SAXS long periods. Crystals with higher SAXS long periods remain stable to higher temperatures, requiring more heat to destabilize the crystalline structure.
In highly oriented polymeric samples such as fibers, those with higher SAXS long periods will remain stable to higher temperatures. Thus the shrinkage, which is a normal effect of the relaxation of the highly oriented polymeric samples, remains low to higher temperatures than in those highly oriented polymeric samples with lower SAXS long periods. In this invention, as is evident from these measurements, the nucleating additive is used in conjunction with a thermal treatment to create fibers with extremely high SAXS long periods of at least 20 nm, or preferably at least 22 nm, which in turn are very stable and exhibit low shrinkage up to very high temperatures.
Furthermore, such fibers may also be colored to provide other aesthetic features for the end user. Thus, the fibers may also comprise coloring agents, such as, for example, pigments, with fixing agents for lightfastness purposes. For this reason, it is desirable to utilize nucleating agents that do not impart visible color or colors to the target fibers. Other additives may also be present, including antistatic agents, brightening compounds, clarifying agents, antioxidants, antimicrobials (preferably silver-based ion-exchange compounds, such as ALPHASAN(copyright) antimicrobials available from Milliken and Company), UV stabilizers, fillers, and the like. Furthermore, any fabrics made from such inventive fibers may be, without limitation, woven, knit, non-woven, in-laid scrim, any combination thereof, and the like. Additionally, such fabrics may include fibers other than the inventive polypropylene fibers, including, without limitation, natural fibers, such as cotton, wool, abaca, hemp, ramie, and the like; synthetic fibers, such as polyesters, polyamides, polyaramids, other polyolefins (including non-low-shrink polypropylene), polylactic acids, and the like; inorganic fibers such as glass, boron-containing fibers, and the like; and any blends thereof.